Substituted tetraarylbenzenes

ABSTRACT

The present invention relates to substances, to electroluminescent device comprising these substances, and to the use thereof.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a national stage application (under 35 U.S.C. §371)of PCT/EP2011/005810, filed Nov. 17, 2011, which claims benefit ofGerman Application No. 10 2010 054 316.0, filed Dec. 13, 2010 which areboth incorporated by reference.

The present invention relates to organic electroluminescent devices andto materials for use in organic electroluminescent devices.

The structure of organic electroluminescent devices (OLEDs) in whichorganic semiconductors are employed as functional materials isdescribed, for example, in U.S. Pat. No. 4,539,507, U.S. Pat. No.5,151,629, EP 0676461 and WO 98/27136. The emitting materials employedhere, besides fluorescent emitters, are increasingly organometalliccomplexes which exhibit phosphorescence (M. A. Baldo et al., Appl. Phys.Lett. 1999, 75, 4-6). For quantum-mechanical reasons, an up to four-foldenergy and power efficiency is possible using organometallic compoundsas phosphorescence emitters. In general, there is still a need forimprovement both in the case of OLEDs which exhibit singlet emission andalso in the case of OLEDs which exhibit triplet emission, in particularwith respect to efficiency, operating voltage and lifetime. Thisapplies, in particular, to OLEDs which emit in the relatively short-waveregion, i.e. green and in particular blue.

The properties of OLEDs are determined not only by the emittersemployed. In particular, the other materials used, such as host andmatrix materials, hole-blocking materials, electron-transport materials,hole-transport materials and electron- or exciton-blocking materials,are also of particular importance here. Improvements in these materialscan thus also result in significant improvements in the OLED properties.

According to the prior art, ketones (for example in accordance with WO2004/093207 or WO 2010/006680) or phosphine oxides (for example inaccordance with WO 2005/003253), inter alia, are used as matrixmaterials for phosphorescent emitters. Further matrix materials inaccordance with the prior art are represented by triazines (for exampleWO 2008/056746, EP 0906947, EP 0908787, EP 0906948).

For fluorescent OLEDs, it is mainly condensed aromatic compounds, inparticular anthracene derivatives, that are used in accordance with theprior art as host materials, especially for blue-emittingelectroluminescent devices, for example 9,10-bis(2-naphthyl)anthracene(U.S. Pat. No. 5,935,721). WO 03/095445 and CN 1362464 disclose9,10-bis(1-naphthyl)anthracene derivatives for use in OLEDs. Furtheranthracene derivatives are disclosed in WO 01/076323, in WO 01/021729,in WO 2004/013073, in WO 2004/018588, in WO 2003/087023 or in WO2004/018587. Host materials based on aryl-substituted pyrenes andchrysenes are disclosed in WO 2004/016575. Host materials based onbenzanthracene derivatives are disclosed in WO 2008/145239. Forhigh-quality applications, it is desirable to have improved hostmaterials available.

However, there is still a need for improvement in the case of the use ofthese host and matrix materials as also in the case of other host andmatrix materials, in particular with respect to the efficiency andlifetime of the device.

Although OLEDs based on small molecules (SMOLEDs) in some cases exhibitfairly good efficiencies, lifetimes and/or operating voltage, thermalvacuum vapour-deposition methods are necessary, which are restricted toa certain device size. For mass production and for larger displays,however, it is desirable to apply the organic materials from solution,for example by means of spin-coating or ink-jet processes, whichadditionally enable the production costs to be reduced. Light-emittingpolymers, oligomers and/or dendrimers are usually used in order toprocess electroluminescent devices from solution. These compounds oftenexhibit good solubility in organic aromatic solvents and have goodfilm-formation properties. A further possibility for improvingprocessability consists in incorporating long alkyl chains into amolecule as solubility-promoting groups. Unfortunately, the devicesprocessed from solution using polymers, oligomers and/or dendrimers ormolecules having alkyl chains usually have worse performance thancomparable small molecules with respect to efficiency, lifetime andoperating voltage.

The object of the present invention is the provision of compounds whichare suitable for use in a fluorescent or phosphorescent OLED, forexample as host and/or matrix material or ashole-transport/electron-blocking material or exciton-blocking materialor as electron-transport or hole-blocking material, and which result ingood device properties on use in an OLED, and the provision of thecorresponding electronic device.

A further object of the present invention consists in the provision ofmolecules which have improved solubility and can therefore be processedfrom solution in the production of a light-emitting device Still afurther object of the present invention consists in the provision ofmolecules which are particularly suitable for producing light-emittingdevices from the gas phase, i.e. providing molecules which can beapplied particularly well by vapour deposition.

Surprisingly, it has been found that certain compounds described ingreater detail below achieve these objects and result in good propertiesof the organic electroluminescent device, in particular with respect tothe lifetime, efficiency and operating voltage. The present inventiontherefore relates to electronic devices, in particular organicelectroluminescent devices, which comprise compounds of this type and tothe corresponding preferred compounds.

The present invention relates to compounds of the general formula (1)

where the following applies to the symbols and indices used:

-   X is on each occurrence, identically or differently, CH or N;-   Y is on each occurrence, identically or differently, CR¹, N, P or    PR¹ ₂;-   n is an integer from 0 to 5, where, if n is greater than or equal to    1, the n substituents Z are bonded to Y═CR¹ and in each case have    replaced the radical R¹ here;-   m is an integer from 0 to 5, where, if m is greater than or equal to    1, the m substituents Z are bonded to Y═CR¹ and in each case have    replaced the radical R¹ here;-   o is an integer from 0 to 5, where, if o is greater than or equal to    1, the o substituents Z are bonded to Y═CR¹ and in each case have    replaced the radical R¹ here;-   P is an integer from 0 to 5, where, if p is greater than or equal to    1, the p substituents Z are bonded to Y═CR¹ and in each case have    replaced the radical R¹ here;    -   where the following condition must be satisfied: m+n+o+p=1, 2, 3        or 4;        and where at least one of the rings A, B, C or D must be        substituted by a substituent Z in the meta position;-   R¹ is, identically or differently on each occurrence, H, D, F, Cl,    Br, I, N(R²)₂, CN, NO₂, Si(R²)₃, B(OR²)₂, C(═O)R², P(═O)(R²)₂,    S(═O)R², S(═O)₂R², OSO₂R², a straight-chain alkyl, alkoxy or    thioalkoxy group having 1 to 40 C atoms or a straight-chain alkenyl    or alkynyl group having 2 to 40 C atoms or a branched or cyclic    alkyl, alkenyl, alkynyl, alkoxy, alkylalkoxy or thioalkoxy group    having 3 to 40 C atoms, each of which may be substituted by one or    more radicals R², where one or more non-adjacent CH₂ groups may be    replaced by R²C═CR², C≡C, Si(R²)₂, Ge(R²)₂, Sn(R²)₂, C═O, C═S, C═Se,    C═NR², P(═O)(R²), SO, SO₂, NR², O, S or CONR² and where one or more    H atoms may be replaced by D, F, Cl, Br, I, CN or NO₂, or an    aromatic or heteroaromatic ring system having 5 to 60 aromatic ring    atoms, which may in each case be substituted by one or more radicals    R², or an aryloxy, arylalkoxy or heteroaryloxy group having 5 to 60    aromatic ring atoms, which may be substituted by one or more    radicals R², or a diarylamino group, diheteroarylamino group or    arylheteroarylamino group having 10 to 40 aromatic ring atoms, which    may be substituted by one or more radicals R², or a combination of    two or more of these groups or a crosslinkable group Q;-   R² is, identically or differently on each occurrence, H, D, F, Cl,    Br, I, N(R³)₂, CN, NO₂, Si(R³)₃, B(OR³)₂, C(═O)R³, P(═O)(R³)₂,    S(═O)R³, S(═O)₂R³, OSO₂R³, a straight-chain alkyl, alkoxy or    thioalkoxy group having 1 to 40 C atoms or a straight-chain alkenyl    or alkynyl group having 2 to 40 C atoms or a branched or cyclic    alkyl, alkenyl, alkynyl, alkoxy, alkylalkoxy or thioalkoxy group    having 3 to 40 C atoms, each of which may be substituted by one or    more radicals R³, where one or more non-adjacent CH₂ groups may be    replaced by R³C═CR³, C≡C, Si (R³)₂, Ge(R³)₂, Sn(R³)₂, C═O, C═S,    C═Se, C═NR³, P(═O)(R³), SO, SO₂, NR³, O, S or CONR³ and where one or    more H atoms may be replaced by D, F, Cl, Br, I, CN or NO₂, or an    aromatic or heteroaromatic ring system having 5 to 60 aromatic ring    atoms, which may in each case be substituted by one or more radicals    R³, or an aryloxy, arylalkoxy or heteroaryloxy group having 5 to 60    aromatic ring atoms, which may be substituted by one or more    radicals R³, or a diarylamino group, diheteroarylamino group or    arylheteroarylamino group having 10 to 40 aromatic ring atoms, which    may be substituted by one or more radicals R³, or a combination of    two or more of these groups; two or more adjacent radicals R² here    may form a mono- or polycyclic, aliphatic or aromatic ring system    with one another;-   R³ is, identically or differently on each occurrence, H, D, F or an    aliphatic, aromatic and/or heteroaromatic hydrocarbon radical having    1 to 20 C atoms, in which, in addition, one or more H atoms may be    replaced by F; two or more substituents R³ here may also form a    mono- or polycyclic, aliphatic or aromatic ring system with one    another;-   Z is on each occurrence, identically or differently, R¹, with the    proviso that at least one of the radicals Z must be an aromatic or    heteroaromatic group having 5 to 60 aromatic ring atoms.

“Crosslinkable group” in the sense of the resent invention means afunctional group which is capable of reacting irreversibly. Acrosslinked material, which is insoluble, is thereby formed. Thecrosslinking can usually be supported by heat or by UV, microwave, X-rayor electron radiation. Due to the high stability of the polymeraccording to the invention, less by-product formation occurs during thecrosslinking. In addition, the crosslinkable groups in the polymeraccording to the invention crosslink very easily, meaning that loweramounts of energy are necessary for the crosslinking (for example <200°C. in the case of thermal crosslinking).

Examples of crosslinkable groups Q are units which contain a doublebond, a triple bond, a precursor which is capable of in-situ formationof a double or triple bond, or a heterocyclic addition-polymerisableradical. Preferred radicals Q include vinyl, alkenyl, preferably ethenyland propenyl, C₄₋₂₀-cycloalkenyl, azide, oxirane, oxetane,di(hydrocarbyl)amino, cyanate ester, hydroxyl, glycidyl ether,C₁₋₁₀-alkyl acrylate, C₁₋₁₀-alkyl methacrylate, alkenyloxy, preferablyethenyloxy, perfluoroalkenyloxy, preferably perfluoroethenyloxy,alkynyl, preferably ethynyl, maleimide, tri(C₁₋₄)-alkylsiloxy andtri(C₁₋₄)-alkylsilyl. Particular preference is given to vinyl andalkenyl.

An aryl group in the sense of this invention contains 6 to 40 C atoms; aheteroaryl group in the sense of this invention contains 1 to 39 C atomsand at least one heteroatom, with the proviso that the sum of C atomsand heteroatoms is at least 5. The heteroatoms are preferably selectedfrom N, O and/or S. An aryl group or heteroaryl group here is taken tomean either a simple aromatic ring, i.e. benzene, or a simpleheteroaromatic ring, for example pyridine, pyrimidine, thiophene, etc.,or a condensed (anellated) aryl or heteroaryl group, for examplenaphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc.Aromatic groups which are linked to one another by a single bond, suchas, for example, biphenyl, are, by contrast, not referred to as aryl orheteroaryl group, but instead as aromatic ring system.

An aromatic ring system in the sense of this invention contains 6 to 60C atoms in the ring system. A heteroaromatic ring system in the sense ofthis invention contains 1 to 59 C atoms and at least one heteroatom inthe ring system, with the proviso that the sum of C atoms andheteroatoms is at least 5. The heteroatoms are preferably selected fromN, O and/or S. For the purposes of this invention, an aromatic orheteroaromatic ring system is intended to be taken to mean a systemwhich does not necessarily contain only aryl or heteroaryl groups, butinstead in which, in addition, a plurality of aryl or heteroaryl groupsmay be linked by a non-aromatic unit, such as, for example, a C, N or Oatom. Thus, for example, systems such as fluorene, 9,9′-spirobifluorene,9,9-diarylfluorene, triarylamine, diaryl ether, stilbene, etc., are alsointended to be taken to be aromatic ring systems for the purposes ofthis invention, as are systems in which two or more aryl groups areinterrupted, for example, by a short alkyl group. Furthermore, systemsin which a plurality of aryl and/or heteroaryl groups are linked to oneanother by a single bond, such as, for example, biphenyl, terphenyl orbipyridine, are intended to be taken to be an aromatic or heteroaromaticring system.

For the purposes of the present invention, an aliphatic hydrocarbonradical or an alkyl group or an alkenyl or alkynyl group, which maytypically contain 1 to 40 or also 1 to 20 C atoms and in which, inaddition, individual H atoms or CH₂ groups may be substituted by theabove-mentioned groups, is preferably taken to mean the radicals methyl,ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl,2-methylbutyl, n-pentyl, s-pentyl, cyclopentyl, n-hexyl, cyclohexyl,n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl,trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl,propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl,heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl,butynyl, pentynyl, hexynyl, heptynyl or octynyl. An alkoxy group having1 to 40 C atoms is preferably taken to mean methoxy, trifluoromethoxy,ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy,n-pentoxy, s-pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexyloxy,n-heptoxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy,pentafluoroethoxy and 2,2,2-trifluoroethoxy. A thioalkyl group having 1to 40 C atoms is taken to mean, in particular, methylthio, ethylthio,n-propylthio, i-propylthio, n-butylthio, i-butylthio, s-butylthio,t-butylthio, n-pentylthio, s-pentylthio, n-hexylthio, cyclohexylthio,n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio,2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio,2,2,2-trifluoroethylthio, ethenylthio, propenylthio, butenylthio,pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio,heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio,ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio,heptynylthio or octynylthio. In general, alkyl, alkoxy or thioalkylgroups in accordance with the present invention may be straight-chain,branched or cyclic, where one or more non-adjacent CH₂ groups may bereplaced by R¹C═CR¹, C≡C, Si(R¹)₂, Ge(R¹)₂, Sn(R¹)₂, C═O, C═S, C═Se,C═NR¹, P(═O)(R¹), SO, SO₂, NR¹, O, S or CONR¹; furthermore, one or moreH atoms may also be replaced by D, F, Cl, Br, I, CN or NO₂, preferablyF, Cl or CN, further preferably F or CN, particularly preferably CN.

An aromatic or heteroaromatic ring system having 5-60 aromatic ringatoms, which may also in each case be substituted by the above-mentionedradicals R¹ or a hydrocarbon radical and which may be linked to thearomatic or heteroaromatic ring system via any desired positions, istaken to mean, in particular, groups derived from benzene, naphthalene,anthracene, benzanthracene, phenanthrene, pyrene, chrysene, perylene,fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl,biphenylene, terphenyl, triphenylene, fluorene, spirobifluorene,dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- ortrans-indenofluorene, cis- or trans-indenocarbazole, cis- ortrans-indolocarbazole, truxene, isotruxene, spirotruxene,spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran,thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole,indole, isoindole, carbazole, pyridine, quinoline, isoquinoline,acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline,benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole,imidazole, benzimidazole, naphthimidazole, phenanthrimidazole,pyridimidazole, pyrazinimidazole, quinoxalinimidazole, oxazole,benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole,1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine,hexaazatriphenylene, benzopyridazine, pyrimidine, benzopyrimidine,quinoxaline, 1,5-diazaanthracene, 2,7-diazapyrene, 2,3-diazapyrene,1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene,4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenoxazine,phenothiazine, fluorubin, naphthyridine, azacarbazole, benzocarboline,phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole,1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole,1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole,1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine,tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine,purine, pteridine, indolizine and benzothiadiazole.

A preferred embodiment of the present invention are compounds of thegeneral formula (2)

where the above definitions apply to the symbols and indices indicated;andq, r, s, t is, independently of one another, either 0 or 1, where,u=q+r+s+t=1, 2, 3, 4.

Preference is furthermore given in the sense of the present invention tocompounds of the formula (3)

where the above definitions apply to the symbols and indices used.

Very preference is given in the sense of the present invention tocompounds of the formula (4)

where the above definitions apply to the symbols and indices used.

Very particularly preferred compounds of the present invention are thoseof the formula (5)

where the above definitions apply to the symbols and indices used.

Especially preferred compounds in the sense of the present invention arethose of the general formula (6)

where the above definitions apply to the symbols and indices used.

In a furthermore preferred embodiment of the present invention,u=q+r+s+t=3.

Preferred embodiments of the present invention are therefore thecompounds of the formula (7) to (9).

where the above definitions apply to the symbols and indices used.

Preference is furthermore given in the sense of the present invention tocompounds of the formula (2) to (6) where u=2.

In a very preferred embodiment of the present invention, u=1 for thecompounds of the formula (2) to (6). The compounds of the formula (10)to (12) represent very preferred embodiments of the present invention.

where the above definitions apply to the symbols and indices used.

In furthermore preferred embodiments of the present invention, X in thecompounds having the formulae (1) to (12) is, identically on eachoccurrence, either CH or N.

It is very particularly preferred if X═N. Particularly preferredembodiments of the present invention are therefore the compounds of theformula (13).

where the above definitions apply to the symbols and indices used.

Furthermore preferred embodiments of the present invention are thecompounds of the formula (14)

where the above definitions apply to the symbols and indices used.

Furthermore preferred embodiments of the present invention are thecompounds of the formula (15)

where the above definitions apply to the symbols and indices used.

In a very particularly preferred embodiment of the present invention,X═CH. Very particularly preferred compounds in the sense of the presentinvention are therefore compounds of the formula (16).

where the above definitions apply to the symbols and indices indicated.

Furthermore preferred compounds in the sense of the present inventionare compounds of the formula (17).

where the above definitions apply to the symbols and indices used.

Furthermore very preferred compounds in the sense of the presentinvention are compounds of the formula (18).

where the above definitions apply to the symbols and indices used.

Furthermore preferred embodiments of the present invention are thecompounds of the formula (19)

where the above definitions apply to the symbols and indices used.

Furthermore preferred embodiments of the present invention are thecompounds of the formula (20)

where the above definitions apply to the symbols and indices used.

In a furthermore preferred embodiment of the present invention,u=q+r+s+t=3.

Preferred embodiments of the present invention are therefore, inparticular, the compounds having the formulae (21) to (23).

where the above definitions apply to the symbols used.

Preference is furthermore given in the sense of the present invention tocompounds of the formula (17) to (20) where u=2.

In a very preferred embodiment of the present invention, u=1, i.e. thecompounds of the formula (24) to (26) represent very preferredembodiments of the present invention.

where the above definitions apply to the symbols used.

A further preferred embodiment of the present invention relates tocompounds of the formulae (1) to (26) which contain only one substituentZ, which is located on one of the rings A to D, but always in the metaposition to the central ring E, and where X═CH and merely in each case amaximum of one Y on each ring A, B, C, D is equal to CR¹ (see formulae(27) to (29)).

where the above definitions apply to the symbols used.

Furthermore preferred embodiments of the compounds (27) to (29) arethose in which, besides the radical Z, only one radical R¹ occurs in themolecule, where the radical R may occur in any possible position of therings A, B, C and D. Particular preference is given here to thecompounds of the formula (30) to (62).

In an especially preferred embodiment of the present invention, thecompound of the formula (1) contains only one substituent Z, which islocated on one of the rings A to D, but always in the meta position tothe central ring E, and where X═CH and Y═CR¹, where R¹═H (see formulae(63) to (65))

In a preferred embodiment of the present invention, Z is, identically ordifferently on each occurrence, H, D, F, Cl, Br, I, N(R²)₂, CN, NO₂,Si(R²)₃, B(OR²)₂, C(═O)R², P(═O)(R²)₂, S(═O)R², S(═O)₂R², OSO₂R², astraight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atomsor a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms or abranched or cyclic alkyl, alkenyl, alkynyl, alkoxy, alkylalkoxy orthioalkoxy group having 3 to 40 C atoms, each of which may besubstituted by one or more radicals R², where one or more non-adjacentCH₂ groups may be replaced by R²C═CR², C≡C, Si(R²)₂, Ge(R²)₂, Sn(R²)₂,C═O, C═S, C═Se, C═NR², P(═O)(R²), SO, SO₂, NR², O, S or CONR² and whereone or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO₂, or anaromatic or heteroaromatic ring system having 5 to 60 aromatic ringatoms, which may in each case be substituted by one or more radicals R²,or an aryloxy, arylalkoxy or heteroaryloxy group having 5 to 60 aromaticring atoms, which may be substituted by one or more radicals R², or adiarylamino group, diheteroarylamino group or arylheteroarylamino grouphaving 10 to 40 aromatic ring atoms, which may be substituted by one ormore radicals R², or a combination of two or more of these groups, withthe proviso that at least one of the radicals Z occurring must be anaromatic or heteroaromatic group having 5 to 60 aromatic ring atoms.

In a furthermore preferred embodiment of the present invention, Z in thecompounds having the formulae (1) to (65) is, identically or differentlyon each occurrence, a straight-chain alkyl, alkoxy or thioalkoxy grouphaving 1 to 20 C atoms or a straight-chain alkenyl or alkynyl grouphaving 2 to 20 C atoms or a branched or cyclic alkyl, alkenyl, alkynyl,alkoxy, alkylalkoxy or thioalkoxy group having 3 to 20 C atoms, each ofwhich may be substituted by one or more radicals R², where one or morenon-adjacent CH₂ groups may be replaced by R²C═CR², C≡C, Si(R²)₂, C═O,C═S, C═NR², P(═O)(R²), SO, SO₂, NR², O, S or CONR² and where one or moreH atoms may be replaced by D, F, Cl, Br, I, CN or NO₂, or an Si(R²)₃group, or an aromatic or heteroaromatic ring system having 5 to 60aromatic ring atoms, which may in each case be substituted by one ormore radicals R², or an arylketo, aryloxy, arylalkoxy, alkylaryloxy orheteroaryloxy group having 5 to 60 aromatic ring atoms, which may besubstituted by one or more radicals R², or a diarylamino group,diheteroarylamino group or arylheteroarylamino group having 10 to 40aromatic ring atoms, which may be substituted by one or more radicalsR², or a combination of two or more of these groups; at least one of theradicals Z occurring here must contain an aromatic or heteroaromaticgroup having 5 to 60 aromatic ring atoms, with the proviso that at leastone of the radicals Z occurring must be an aromatic or heteroaromaticgroup having 5 to 60 aromatic ring atoms.

In a very preferred embodiment of the present invention, Z in thecompounds having the formulae (1) to (65) is, identically or differentlyon each occurrence, a straight-chain alkyl or alkoxy group having 1 to20 C atoms or a straight-chain alkenyl or alkynyl group having 2 to 20 Catoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy oralkylalkoxy group having 3 to 20 C atoms, each of which may besubstituted by one or more radicals R², where one or more non-adjacentCH₂ groups may be replaced by R²C═CR², C≡C, Si(R²)₂, C═O, C═S, C═NR²,P(═O)(R²), SO, SO₂, NR², O, S or CONR² and where one or more H atoms maybe replaced by D, F, Cl, Br, I, CN or NO₂, or an Si(R²)₃ group, or anaromatic or heteroaromatic ring system having 5 to 60 aromatic ringatoms, which may in each case be substituted by one or more radicals R²,or an arylketo, aryloxy, arylalkoxy, alkylaryloxy or heteroaryloxy grouphaving 5 to 60 aromatic ring atoms, which may be substituted by one ormore radicals R², or a diarylamino group, diheteroarylamino group orarylheteroarylamino group having 10 to 40 aromatic ring atoms, which maybe substituted by one or more radicals R², or a combination of two ormore of these groups; at least one of the radicals Z occurring here mustcontain an aromatic or heteroaromatic group having 5 to 60 aromatic ringatoms, with the proviso that at least one of the radicals Z occurringmust be an aromatic or heteroaromatic group having 5 to 60 aromatic ringatoms.

In a further very preferred embodiment of the present invention, atleast one of the radicals Z occurring in the compounds having theformulae (1) to (65) is an aromatic or heteroaromatic group having 5 to60 aromatic ring atoms, where the group of the aromatic andheteroaromatic groups having 5 to 60 ring atoms also include condensedaromatic and heteroaromatic ring systems.

If the compound of the formula (1) to (65) is used as matrix materialfor a phosphorescent electroluminescent device, Z is preferably selectedfrom the group consisting of benzene, pyridine, pyrimidine, pyridazine,pyrazine, triazine, pyrrole, thiophene, furan, naphthalene, quinoline,isoquinoline, quinoxaline, indole, benzothiophene or benzofuran, each ofwhich may be substituted by one or more radicals R¹. Particularlypreferred groups Z are built up from in each case one or more groupsbenzene, pyridine, pyrimidine, pyridazine, pyrazine or triazine, each ofwhich may be substituted by one or more radicals R¹, in particularbenzene, which may be substituted by one or more radicals R¹. Furtherpreferred groups Z for use as triplet matrix material are triphenylene,carbazole, indenocarbazole, indolocarbazole, each of which may besubstituted by one or more radicals R¹. Likewise suitable arecombinations of the aryl and heteroaryl groups mentioned as preferred.If the compound of the formula (1) to (65) is used in another function,for example as singlet host material and/or electron-transport material,preferred groups Z may also contain larger condensed aryl or heteroarylgroups, for example anthracene, pyrene or perylene, each of which may besubstituted by one or more radicals R¹.

If the compounds of the formula (1) to (65) are employed as hostmaterials for fluorescent emitters, Z is then preferably an anthracene,benzanthracene, pyrene, perylene, indenofluorene, fluorene,spirobifluorene, phenanthrene, dihydrophenanthrene, thiophene,imidazoles, each of which may be substituted by one or more radicals R¹.

In a particularly preferred embodiment of the invention, Z is selectedfrom the group consisting of the units of the following formulae (66) to(80).

where the symbols used have the meanings given above.

In a preferred embodiment of the present invention, R¹ is, identicallyor differently on each occurrence, H, D, F, Cl, Br, I, N(R²)₂, CN, NO₂,Si(R²)₃, B(OR²)₂, C(═O)R², P(═O)(R²)₂, S(═O)R², S(═O)₂R², OSO₂R², astraight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atomsor a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms or abranched or cyclic alkyl, alkenyl, alkynyl, alkoxy, alkylalkoxy orthioalkoxy group having 3 to 40 C atoms, each of which may besubstituted by one or more radicals R², where one or more non-adjacentCH₂ groups may be replaced by R²C═CR², C═C, Si(R²)₂, Ge(R²)₂, Sn(R²)₂,C═O, C═S, C═Se, C═NR², P(═O)(R²), SO, SO₂, NR², O, S or CONR² and whereone or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO₂, or anaromatic or heteroaromatic ring system having 5 to 60 aromatic ringatoms, which may in each case be substituted by one or more radicals R²,or an aryloxy, arylalkoxy or heteroaryloxy group having 5 to 60 aromaticring atoms, which may be substituted by one or more radicals R², or adiarylamino group, diheteroarylamino group or arylheteroarylamino grouphaving 10 to 40 aromatic ring atoms, which may be substituted by one ormore radicals R², or a combination of two or more of these groups.

It is furthermore preferred in the sense of the present invention for R¹to be, identically or differently on each occurrence, H, D, F, Cl, Br,I, N(R²)₂, CN, a straight-chain alkyl, alkoxy or thioalkoxy group having1 to 40 C atoms or a straight-chain alkenyl or alkynyl group having 2 to40 C atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy,alkylalkoxy or thioalkoxy group having 3 to 40 C atoms, each of whichmay be substituted by one or more radicals R², where one or morenon-adjacent CH₂ groups may be replaced by R²C═CR², C≡C, Si(R²)₂,Sn(R²)₂, C═O, C═S, C═NR², P(═O)(R²), SO₂, NR², O, S or CONR² and whereone or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO₂, or anaromatic or heteroaromatic ring system having 5 to 60 aromatic ringatoms, which may in each case be substituted by one or more radicals R²,or an aryloxy, arylalkoxy or heteroaryloxy group having 5 to 60 aromaticring atoms, which may be substituted by one or more radicals R², or adiarylamino group, diheteroarylamino group or arylheteroarylamino grouphaving 10 to 40 aromatic ring atoms, which may be substituted by one ormore radicals R², or a combination of two or more of these groups.

If the compound of the formulae (1) to (65) is employed as tripletmatrix material, in particular for emitters which emit green or bluelight, and the radical R¹ stands for an aromatic or heteroaromatic ringsystem, it is preferred for the latter to contain no aryl groups havingmore than two condensed aryl rings. This preference can be explained bythe low triplet level of aryl groups having more than two condensed arylrings, making compounds of this type less suitable as triplet matrixmaterial. The aromatic or heteroaromatic ring system particularlypreferably contains no condensed aryl groups. Preferred aromatic orheteroaromatic ring systems R¹ for use as triplet matrix material aretherefore built up from in each case one or more of the groups benzene,pyridine, pyrimidine, pyridazine, pyrazine, triazine, pyrrole,thiophene, furan, naphthalene, quinoline, isoquinoline, quinoxaline,indole, benzothiophene or benzofuran, each of which may be substitutedby one or more radicals R². Particularly preferred groups Z are built upfrom in each case one or more groups benzene, pyridine, pyrimidine,pyridazine, pyrazine or triazine, each of which may be substituted byone or more radicals R², in particular benzene, which may be substitutedby one or more radicals R². Further preferred groups R¹ for use astriplet matrix material are triphenylene and carbazole. Preference islikewise given to combinations of the aryl and heteroaryl groupsmentioned as preferred. If the compound of the formula (1) is used inanother function, for example as singlet host material and/orelectron-transport material, preferred groups R¹ may also contain largercondensed aryl or heteroaryl groups, for example anthracene, pyrene orperylene, each of which may be substituted by one or more radicals R².

In a very particularly preferred embodiment of the present invention, atleast one of the radicals Z occurring in the compounds having the is anaromatic or heteroaromatic group having 5 to 60 aromatic ring atoms,where the aromatic and heteroaromatic group merely includes naphtylgroups as condensed aromatic groups, but not other condensed aromaticand heteroaromatic groups.

In a very particularly preferred embodiment of the present invention, atleast one of the radicals Z occurring in the compounds having theformula (1) to (65) is an aromatic or heteroaromatic group having 5 to60 aromatic ring atoms, where condensed aromatic and heteroaromaticgroups are not included.

In a very preferred embodiment of the present invention, the radical Zis selected from the formulae (81) to (289), where the formulaeindicated may themselves be substituted by one or more radicals R³,which may be identical or different on each occurrence and with theproviso that at least one of the radicals Z must be an aromatic orheteroaromatic group having 5 to 60 aromatic ring atoms.

where the dash denotes the position of the linking of the radical Z.

The compounds of the formula (1) can also be used as monomers of thegeneral formula (290) for the preparation of oligomers, dendrimers andpolymers. In this case, the polymer containing the compound of theformula (1) can be both a homopolymer and also a copolymer.

The present invention accordingly also relates to monomers of thegeneral formula (290)

where the above definitions apply to the symbols and indices used (seeformula (1))and at least one of the rings A, B, C or D must be substituted by asubstituent Z in the meta positionand with the proviso that at least one of the radicals Z must be anaromatic or heteroaromatic group having 5 to 60 aromatic ring atomsand where the substituent or substituents Z in each case replace theradicals R¹ andtwo or more of the radicals R¹ are identically or differently functionalgroups which polymerise under conditions of the C—C or C—N linkingreactions.

The functional groups are preferably selected from Cl, Br, I,O-tosylate, O-triflate, O—SO₂R², B(OR²)₂ and Sn(R²)₃, particularlypreferably from Br, I and B(OR²)₂, where R² is on each occurrence,identically or differently, H, an aliphatic or aromatic hydrocarbonradical having 1 to 20 C atoms, and where two or more radicals R² mayalso form a ring system with one another.

The monomers may furthermore, as described above, contain crosslinkablegroups Q, so that the polymers containing the monomers of the formula(290) can be crosslinked.

The compounds of the formula (1) according to the invention where X═CHare synthesised by palladium-catalysed cross-couplings on thecorrespondingly halogenated basic structures having the general formula(291).

where the above definitions apply to the symbols and indices used. Thebasic structures can be prepared from pyrylium salts by generalprocesses correspondingly to the following scheme (Journal f. Prakt.Chemie 1987, 329, 6, 975-984).

Symmetrically substituted compounds of the formula (1) according to theinvention where X═N are synthesised by palladium-catalysedSuzuki-Miyaura couplings on commercially available2,4,5,6-tetrachloropyrimidine (Adv. Synth. Catal. 2010, 352, 1429-1433).

Asymmetrically substituted compounds of the formula (1) according to theinvention where X═N are preferably synthesised by borontrifluoride-catalysed [2+2′+2′]cycloaddition of alkynes and nitriles(Synthesis 1983, 9, 717-718) in accordance with the following scheme:

A further possibility for the preparation of asymmetrically substitutedcompounds of the formula (1) according to the invention where X═N is thepreparation process described in Tetrahedron Letters 2005, 46, 1663-1665and outlined in the following scheme.

where the radicals Ar, Ar¹, Ar², Ar³ and Ar⁴ stand for the substitutedor unsubstituted aromatic radicals A, B, C and D of the compounds of theformulae (1) to (15).

The present invention therefore also relates to the preparation of thecompounds according to the invention by one of the above processes.

Examples of compounds in accordance with the embodiments mentionedabove, as can preferably be employed in organic electronic devices, arethe compounds of the following structures (298) to (425).

The compounds of the formula (1) can be used in an electronic device. Anelectronic device here is taken to mean a device which comprises atleast one layer which comprises at least one organic compound. However,the component here may also comprise inorganic materials or also layersbuilt up entirely from inorganic materials.

The electronic device is preferably selected from the group consistingof organic electroluminescent devices (OLEDs), organic integratedcircuits (O-ICs), organic field-effect transistors (O-FETs), organicthin-film transistors (O-TFTs), organic light-emitting transistors(O-LETs), organic solar cells (O-SCs), organic optical detectors,organic photoreceptors, organic field-quench devices (O-FQDs),light-emitting electrochemical cells (LECs), organic laser diodes(O-lasers), “organic plasmon emitting devices” (D. M. Koller et al.,Nature Photonics 2008, 1-4) and electrophotography devices, preferablyorganic electroluminescent devices (OLEDs), particularly preferablyphosphorescent OLEDs.

The organic electroluminescent device comprises a cathode, an anode andat least one emitting layer. Apart from these layers, it may alsocomprise further layers, for example in each case one or morehole-injection layers, hole-transport layers, hole-blocking layers,electron-transport layers, electron-injection layers, exciton-blockinglayers and/or charge-generation layers. It is likewise possible forinterlayers, which have, for example, an exciton-blocking function, tobe introduced between two emitting layers. However, it should be pointedout that each of these layers does not necessarily have to be present. Apossible layer structure is, for example, the following:cathode/EML/interlayer/buffer layer/anode, where EML represents theemitting layer. The organic electroluminescent device here may compriseone emitting layer or a plurality of emitting layers. If a plurality ofemission layers are present, these preferably have in total a pluralityof emission maxima between 380 nm and 750 nm, resulting overall in whiteemission, i.e. various emitting compounds which are able to fluoresce orphosphoresce are used in the emitting layers. Particular preference isgiven to three-layer systems, where the three layers exhibit blue, greenand orange or red emission (for the basic structure see, for example, WO2005/011013). Furthermore, an optical coupling-out layer may be appliedto one or both of the electrodes.

The compound in accordance with the above-mentioned embodiments can beemployed in various layers, depending on the precise structure.Preference is given to an organic electroluminescent device comprisingone of the compounds of the formula (1) as host or matrix forfluorescent or phosphorescent emitters, in particular for phosphorescentemitters, and/or in a hole-blocking layer and/or in anelectron-transport layer and/or in an electron-blocking orexciton-blocking layer and/or in a hole-transport layer and/or in anoptical coupling-out layer. The above-mentioned preferred embodimentsalso apply to the use of the materials in organic electronic devices.

In a preferred embodiment of the invention, the compound of the formula(1) as host or matrix material for a fluorescent or phosphorescentcompound in an emitting layer. The organic electroluminescent devicehere may comprise one emitting layer or a plurality of emitting layers,where at least one emitting layer comprises at least one compoundaccording to the invention as host or matrix material.

If the compound of the formula (1) is employed as matrix material for anemitting compound in an emitting layer, it is preferably employed incombination with one or more phosphorescent materials (tripletemitters). Phosphorescence in the sense of this invention is taken tomean the luminescence from an excited state of relatively high spinmultiplicity, i.e. a spin state>1, very preferably from an excitedtriplet and/or quintet state and very particularly preferably from atriplet state. For the purposes of this application, all luminescentcomplexes containing metals from the second and third transition-metalseries, in particular all iridium and platinum complexes, and allluminescent copper complexes are to be regarded as phosphorescentcompounds.

A further preferred embodiment of the present invention is the use ofthe compound of the formula (1) as matrix material for a phosphorescentemitter in combination with a further matrix material. Particularlysuitable matrix materials which can be employed in combination with thecompounds of the formula (1) according to the invention are aromaticketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones,for example in accordance with WO 2004/013080, WO 2004/093207, WO2006/005627 or WO 2010/006680, triarylamines, carbazole derivatives, forexample CBP (N,N-biscarbazolylbiphenyl) or the carbazole derivativesdisclosed in WO 2005/039246, US 2005/0069729, JP 2004/288381, EP 1205527or WO 2008/086851, indolocarbazole derivatives, for example inaccordance with WO 2007/063754 or WO 2008/056746, azacarbazolederivatives, for example in accordance with EP 1617710, EP 1617711, EP1731584, JP 2005/347160, bipolar matrix materials, for example inaccordance with WO 2007/137725, silanes, for example in accordance withWO 2005/111172, azaboroles or boronic esters, for example in accordancewith WO 2006/117052, triazine derivatives, for example in accordancewith WO 2010/015306, WO 2007/063754 or WO 2008/056746, zinc complexes,for example in accordance with EP 652273 or WO 2009/062578, diazasiloleor tetraazasilole derivatives, for example in accordance with theunpublished application DE 102008056688.8, diazaphosphole derivatives,for example in accordance with the unpublished application DE102009022858.6, or indenocarbazole derivatives, for example inaccordance with the unpublished applications DE 102009023155.2 and DE102009031021.5.

Preference is furthermore given for the purposes of the presentinvention to mixtures consisting of more than two matrix materials,where at least one of the matrix materials is one of the compoundsaccording to the invention. Further matrix materials which can beemployed in combination with the compounds according to the inventionare in principle all matrix materials, where preferred matrix materialsare those mentioned above.

Finally, mixtures comprising two or more of the compounds according tothe invention as matrix material are very particularly preferred.

Suitable phosphorescent compounds (triplet emitters) are, in particular,compounds which emit light o radiation, for example in the visibleregion and/or ultraviolet region and/or in the infrared region, onsuitable excitation and in addition contain at least one atom having anatomic number greater than 20, preferably greater than 38 and less than84, particularly preferably greater than 56 and less than 80. Thephosphorescent emitters used are preferably compounds which containcopper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium,iridium, palladium, platinum, silver, gold or europium, in particularcompounds which contain iridium or platinum.

Examples of the emitters described above are revealed by theapplications WO 00/70655, WO 2001/41512, WO 2002/02714, WO 2002/15645,EP 1191613, EP 1191612, EP 1191614, WO 2005/033244, WO 2005/019373 andUS 2005/0258742. In general, all phosphorescent complexes as used inaccordance with the prior art for phosphorescent OLEDs and as are knownto the person skilled in the art in the area of organicelectroluminescence are suitable, and the person skilled in the art willbe able to use further phosphorescent complexes without inventive step.

The matrix materials according to the invention or the mixturesdescribed above comprising one or more of the matrix materials accordingto the invention can be employed as matrix material for individualemitters or for mixtures of emitters.

In general, all phosphorescent complexes as are used in accordance withthe prior art for phosphorescent OLEDs and as are known to the personskilled in the art in the area of organic electroluminescence aresuitable, and the person skilled in the art will be able to use furtherfluorescent compounds without inventive step.

Phosphorescent metal complexes preferably contain Ir, Ru, Pd, Pt, Os orRe. Preferred ligands for phosphorescent metal complexes are2-phenylpyridine derivatives, 7,8-benzoquinoline derivatives,2-(2-thienyl)pyridine derivatives, 2-(1-naphthyl)pyridine derivatives or2-phenylquinoline derivatives. All these compounds may be substituted,for example by fluoro, cyano and/or trifluoromethyl substituents forblue. Auxiliary ligands are preferably acetylacetonate or picolinicacid.

Particularly suitable are complexes of Pt or Pd with tetradentateligands, (US 2007/0087219), Pt-porphyrin complexes having an enlargedring system (US2009/0061681 A1) and Ir complexes, for example2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphyrin-Pt(II),tetraphenyl-Pt(II) tetrabenzoporphyrin (US 2009/0061681),cis-bis(2-phenylpyridinato-N,C²′)Pt(II),cis-bis(2-(2′-thienyl)pyridinato-N,C³′)Pt(II),cis-bis(2-(2′-thienyl)quinolinato-N,C⁵′)Pt(II),(2-(4,6-difluorophenyl)pyridinato-N,C²′)Pt(II) (acetylacetonate), ortris(2-phenylpyridinato-N,C²′)Ir(III) (=Ir(ppy)₃, green),bis(2-phenylpyridinato-N,C²)Ir(III) (acetylacetonate) (=Ir(ppy)₂acetylacetonate, green, US 2001/0053462 A1, Baldo, Thompson et al.Nature 403, (2000), 750-753),bis(1-phenylisoquinolinato-N,C²′)(2-phenylpyridinato-N,C²′)iridium(III),bis(2-phenylpyridinato-N,C²′)(1-phenylisoquinolinato-N,C²′)iridium(II),bis(2-(2′-benzothienyl)pyridinato-N,C³′)iridium(III) (acetylacetonate),bis(2-(4′,6′-difluorophenyl)pyridinato-N,C²′)iridium(III) (piccolinate)(FIrpic, blue), bis(2-(4′,6′-difluorophenyl)pyridinato-N,C²′)Ir(III)(tetrakis(1-pyrazolyl)borate),tris(2-(biphenyl-3-yl)-4-tert-butylpyridine)iridium(III),(ppz)₂Ir(5phdpym) (US 2009/0061681 A1), (45ooppz)₂Ir(5phdpym) (US2009/0061681 A1), derivatives of 2-phenylpyridine-Ir complexes, such as,for example, PQIr (=iridium(III)bis(2-phenylquinolyl-N,C²′)acetylacetonate),tris(2-phenylisoquinolinato-N,C)Ir(III) (red),bis(2-(2′-benzo[4,5-a]thienyl)pyridinato-N,C³)Ir (acetylacetonate)([Btp₂Ir(acac)], red, Adachi et al. Appl. Phys. Lett. 78 (2001),1622-1624).

Likewise suitable are complexes of trivalent lanthanides, such as, forexample, Tb³⁺ and Eu³⁺ (J. Kido et al. Appl. Phys. Lett. 65 (1994),2124, Kido et al. Chem. Lett. 657, 1990, US 2007/0252517 A1) orphosphorescent complexes of Pt(II), Ir(I), Rh(I) withmaleonitriledithiolate (Johnson et al., JACS 105, 1983, 1795), Re(I)tricarbonyl-diimine complexes (Wrighton, JACS 96, 1974, 998, interalia), Os(II) complexes with cyano ligands and bipyridyl orphenanthroline ligands (Ma et al., Synth. Metals 94, 1998, 245).

Further phosphorescent emitters having tridentate ligands are describedin U.S. Pat. No. 6,824,895 and U.S. Ser. No. 10/729,238. Red-emittingphosphorescent complexes are found in U.S. Pat. No. 6,835,469 and U.S.Pat. No. 6,830,828.

If the compound of the formula (1) according to the invention isemployed as host material for an emitting compound in an emitting layer,it is preferably employed in combination with one or more fluorescentmaterials (singlet emitters). Fluorescence in the sense of thisinvention is taken to mean the luminescence from an excited state havinglow spin multiplicity, i.e. from a spin state S=1.

A further preferred embodiment of the present invention is the use ofthe compounds of the formula (1) according to the invention as hostmaterial for a fluorescent emitter in combination with a further hostmaterial. Particularly suitable host materials which can be employed incombination with the compounds of the formula (1) are selected from theclasses of the oligoarylenes (for example2,2′,7,7-tetraphenylspirobifluorene in accordance with EP 676461 ordinaphthylanthracene), in particular the oligoarylenes containingcondensed aromatic groups, such as, for example, anthracene,benzanthracene, benzophenanthrene (DE 102009005746.3, WO 2009/069566),phenanthrene, tetracene, coronene, chrysene, fluorene, spirofluorene,perylene, phthaloperylene, naphthaloperylene, decacyclene, rubrene, theoligoarylenevinylenes (for exampleDPVBi=4,4′-bis(2,2-diphenylethenyl)-1,1′-biphenyl) or spiro-DPVBi inaccordance with EP 676461), the polypodal metal complexes (for examplein accordance with WO 2004/081017), in particular metal complexes of8-hydroxyquinoline, for example Alq₃ (=aluminium(III)tris(8-hydroxyquinoline)) orbis(2-methyl-8-quinolinolato)-4-(phenylphenolinolato)aluminium, alsowith imidazole chelate (US 2007/0092753 A1) and the quinoline/metalcomplexes, aminoquinoline/metal complexes, benzoquinoline/metalcomplexes, the hole-conducting compounds (for example in accordance withWO 2004/058911), the electron-conducting compounds, in particularketones, phosphine oxides, sulfoxides, etc. (for example in accordancewith WO 2005/084081 and WO 2005/084082), the atropisomers (for examplein accordance with WO 2006/048268), the boronic acid derivatives (forexample in accordance with WO 2006/117052) or the benzanthracenes (forexample in accordance with DE 102007024850, WO 2008/145239).

Particularly preferred host materials are selected from the classes ofthe oligoarylenes, comprising naphthalene, anthracene, benzanthraceneand/or pyrene or atropisomers of these compounds, the ketones, thephosphine oxides and the sulfoxides. Very particularly preferred hostmaterials are selected from the classes of the oligoarylenes, comprisinganthracene, benzanthracene and/or pyrene or atropisomers of thesecompounds. An oligoarylene in the sense of this invention is intended tobe taken to mean a compound in which at least three aryl or arylenegroups are bonded to one another.

Preference is furthermore given for the purposes of the presentinvention to mixtures consisting of more than two host materials, whereat least one of the host materials is one of the compounds according tothe invention. Further host materials which can be employed incombination with the compounds according to the invention are inprinciple all host materials, where preferred host materials are thosementioned above.

Finally, mixtures comprising two or more of the compounds according tothe invention as host material are very particularly preferred.

Suitable fluorescent compounds (singlet emitters) are, in particular,compounds which emit light or radiation on suitable excitation, forexample in the visible region and/or ultraviolet region and/or in theinfrared region.

Preferred dopants (emitters) are selected from the class of themonostyrylamines, the distyrylamines, the tristyrylamines, thetetrastyrylamines, the styrylphosphines, the styryl ethers and thearylamines.

A monostyrylamine is taken to mean a compound which contains onesubstituted or unsubstituted styryl group and at least one, preferablyaromatic, amine. A distyrylamine is taken to mean a compound whichcontains two substituted or unsubstituted styryl groups and at leastone, preferably aromatic, amine. A tristyrylamine is taken to mean acompound which contains three substituted or unsubstituted styryl groupsand at least one, preferably aromatic, amine. A tetrastyrylamine istaken to mean a compound which contains four substituted orunsubstituted styryl groups and at least one, preferably aromatic,amine. The styryl groups are particularly preferably stilbenes, whichmay also be further substituted. Corresponding phosphines and ethers aredefined analogously to the amines. An arylamine or an aromatic amine inthe sense of this invention is taken to mean a compound which containsthree substituted or unsubstituted aromatic or heteroaromatic ringsystems bonded directly to the nitrogen. At least one of these aromaticor heteroaromatic ring systems is preferably a condensed ring system,preferably having at least 14 aromatic ring atoms. Preferred examplesthereof are aromatic anthracenamines, aromatic anthracenediamines,aromatic pyrenamines, aromatic pyrenediamines, aromatic chrysenamines oraromatic chrysenediamines. An aromatic anthracenamine is taken to mean acompound in which one diarylamino group is bonded directly to ananthracene group, preferably in the 9-position. An aromaticanthracenediamine is taken to mean a compound in which two diarylaminogroups are bonded directly to an anthracene group, preferably in the2,6- or 9,10-position. Aromatic pyrenamines, pyrenediamines,chrysenamines and chrysenediamines are defined analogously thereto,where the diarylamino groups are preferably bonded to the pyrene in the1-position or in the 1,6-position.

Further preferred dopants are selected from indenofluorenamines orindenofluorenediamines, for example in accordance with WO 2006/122630,benzoindenofluorenamines or benzoindenofluorenediamines, for example inaccordance with WO 08/006,449, and dibenzoindenofluorenamines ordibenzoindenofluorenediamines, for example in accordance with WO07/140,847.

Examples of dopants from the class of the styrylamines are substitutedor unsubstituted tristilbenamines or the dopants described in WO2006/000388, WO 2006/058737, WO 2006/000389, WO 2007/065549 and WO2007/115610. Distyrylbenzene and distyrylbiphenyl derivatives aredescribed in U.S. Pat. No. 5,121,029. Further styrylamines can be foundin US 2007/0122656 A1.

Further preferred dopants are selected from derivatives of naphthalene,anthracene, tetracene, benzanthracene, benzophenanthrene (DE 102009005746.3), fluorene, fluoranthene, periflanthene, indenoperylene,phenanthrene, perylene (US 2007/0252517), pyrene, chrysene, decacyclene,coronene, tetraphenylcyclopentadiene, pentaphenylcyclopentadiene,fluorene, spirofluorene, rubrene, coumarine (U.S. Pat. No. 4,769,292,U.S. Pat. No. 6,020,078, US 2007/0252517), pyran, oxazole, benzoxazole,benzothiazole, benzimidazole, pyrazine, cinnamic acid esters,diketopyrrolopyrrole, acridone and quinacridone (US 2007/0252517).

Of the anthracene compounds, particular preference is given to9,10-substituted anthracenes, such as, for example,9,10-diphenylanthracene and 9,10-bis(phenylethynyl)anthracene.1,4-Bis(9′-ethynylanthracenyl)benzene is also a preferred dopant.

Preference is likewise given to derivatives of rubrene, coumarine,rhodamine, quinacridone, such as, for example, DMQA(═N,N′-dimethylquinacridone), dicyanomethylenepyran, such as, forexample, DCM(=4-(dicyanoethylene)-6-(4-dimethylaminostyryl-2-methyl)-4H-pyran),thiopyran, polymethine, pyrylium and thiapyrylium salts, periflantheneand indenoperylene.

Blue fluorescent emitters are preferably polyaromatic compounds, suchas, for example, 9,10-di(2-naphthylanthracene) and other anthracenederivatives, derivatives of tetracene, xanthene, perylene, such as, forexample, 2,5,8,11-tetra-t-butylperylene, phenylene, for example4,4′-bis(9-ethyl-3-carbazovinylene)-1,1′-biphenyl, fluorene,fluoranthene, arylpyrenes (U.S. Ser. No. 11/097,352), arylenevinylenes(U.S. Pat. No. 5,121,029, U.S. Pat. No. 5,130,603), derivatives ofrubrene, coumarine, rhodamine, quinacridone, such as, for example, DMQA,dicyanomethylenepyran, such as, for example, DCM, thiopyrans,polymethine, pyrylium and thiapyrylium salts, periflanthene,indenoperylene, bis(azinyl)imine-boron compounds (US 2007/0092753 A1),bis(azinyl)methene compounds and carbostyryl compounds.

Further preferred blue fluorescent emitters are described in C. H. Chenet al.: “Recent developments in organic electroluminescent materials”Macromol. Symp. 125, (1997) 1-48 and “Recent progress of molecularorganic electroluminescent materials and devices” Mat. Sci. and Eng. R,39 (2002), 143-222.

Further preferred blue-fluorescent emitters are the hydrocarbonsdisclosed in the application DE 102008035413.

The host materials according to the invention or the mixtures describedabove comprising one or more of the host materials according to theinvention can be employed as host material for individual emitters orfor mixtures of emitters.

The mixture of the compound(s) according to the invention and theemitting (fluorescent and/or phosphorescent) compound comprises between99 and 1% by weight, preferably between 98 and 10% by weight,particularly preferably between 97 and 60% by weight, in particularbetween 95 and 80% by weight, of the compound of the formula (1), basedon the entire mixture comprising emitter and matrix or host material.Correspondingly, the mixture comprises between 1 and 99% by weight,preferably between 2 and 90% by weight, particularly preferably between3 and 40% by weight, in particular between 5 and 20% by weight, of theemitter, based on the entire mixture comprising emitter and matrix orhost material.

In a further embodiment of the invention, the organic electroluminescentdevice according to the invention does not comprise a separatehole-injection layer and/or hole-transport layer and/or hole-blockinglayer and/or electron-transport layer, i.e. the emitting layer isdirectly adjacent to the hole-injection layer or the anode, and/or theemitting layer is directly adjacent to the electron-transport layer orthe electron-injection layer or the cathode, as described, for example,in WO 2005/053051. It is furthermore possible to use a metal complexwhich is identical or similar to the metal complex in the emitting layerdirectly adjacent to the emitting layer as hole-transport orhole-injection material, as described, for example, in WO 2009/030981.

In a further preferred embodiment of the invention, the compound of theformula (1) is employed as electron-transport material in anelectron-transport or electron-injection layer. The emitting layer heremay be fluorescent or phosphorescent. If the compound is employed aselectron-transport material, it may be preferred for it to be doped, forexample with alkali-metal complexes, such as, for example, Liq (lithiumhydroxyquinolinate), or with alkali-metal salts, such as, for example,LiF.

In still a further preferred embodiment of the invention, the compoundsof the formula (1) according to the invention are employed in ahole-blocking layer. A hole-blocking layer is taken to mean a layerwhich is directly adjacent to an emitting layer on the cathode side.

In still a further embodiment of the invention, the compounds of theformula (1) are employed in a hole-transport layer or in anelectron-blocking layer or exciton-blocking layer.

It is furthermore possible to use the compounds of the formula (1) bothin a hole-blocking layer or electron-transport layer and also as matrixin an emitting layer or both in a hole-transport layer orexciton-blocking layer and also as matrix in an emitting layer.

In the further layers of the organic electroluminescent device accordingto the invention, all materials as are usually employed in accordancewith the prior art can be used. The person skilled in the art willtherefore be able to employ, without inventive step, all materials knownfor organic electroluminescent devices in combination with the compoundsof the formula (1) according to the invention.

The present invention therefore also relates to compositions comprisingat least one of the compounds according to the invention and a furtherorganically functional material selected from the group of the emitters,host materials, matrix materials, electron-transport materials (ETM),electron-injection materials (EIM), hole-transport materials (HTM),hole-injection materials (HIM), electron-blocking materials (EBM),hole-blocking materials (HBM), exciton-blocking materials (ExBM),particularly preferably emitters and very particularly preferablyfluorescent and/or phosphorescent emitters.

Preference is furthermore given to an organic electroluminescent device,characterised in that one or more layers are coated by means of asublimation process, in which the materials are vapour-deposited invacuum sublimation units at an initial pressure of less than 10⁻⁵ mbar,preferably less than 10⁻⁶ bar. However, it is also possible for theinitial pressure to be even lower, for example less than 10⁻⁷ mbar.

Preference is likewise given to an organic electroluminescent device,characterised in that one or more layers are coated by means of the OVPD(organic vapour phase deposition) process or with the aid of carrier-gassublimation, in which the materials are applied at a pressure between10⁻⁵ mbar and 1 bar. A special case of this process is the OVJP (organicvapour jet printing) process, in which the materials are applieddirectly through a nozzle and thus structured (for example M. S. Arnoldet al., Appl. Phys. Lett. 2008, 92, 053301).

Preference is furthermore given to an organic electroluminescent device,characterised in that one or more layers are produced from solution,such as, for example, by spin coating, or by means of any desiredprinting process, such as, for example, screen printing, flexographicprinting, offset printing, LITI (light induced thermal imaging, thermaltransfer printing), ink-jet printing or nozzle printing. Solublecompounds, which are obtained, for example, by suitable substitution,are necessary for this purpose. These processes are also suitable, inparticular, for oligomers, dendrimers and polymers.

A further embodiment of the present invention relates to formulationscomprising one or more of the compounds according to the invention andone or more solvents. The formulation is highly suitable for theproduction of layers from solution.

Suitable and preferred solvents are, for example, toluene, anisole,xylenes, methyl benzoate, dimethylanisoles, trimethylbenzenes, tetralin,veratrols, tetrahydrofuran, chlorobenzene or dichlorobenzenes andmixtures thereof.

Likewise possible are hybrid processes, in which, for example, one ormore layers are applied from solution and one or more other layers areapplied by vacuum vapour deposition.

These processes are generally known to the person skilled in the art andcan be applied by him without inventive step to organicelectroluminescent devices comprising the compounds according to theinvention.

The organic electroluminescent device according to the invention can beused, for example, in displays or for lighting purposes, but also formedical or cosmetic applications.

The invention therefore furthermore relates to the use of the compoundsaccording to the invention in an electronic device.

The compounds according to the invention are suitable for use inlight-emitting devices. These compounds can thus be employed in a veryversatile manner. Some of the main areas of application here are displayor lighting technologies. It is furthermore particularly advantageous toemploy the compounds and devices comprising these compounds in the areaof phototherapy.

The present invention therefore furthermore relates to the use of thecompounds according to the invention and devices comprising thecompounds for the treatment, prophylaxis and diagnosis of diseases. Thepresent invention still furthermore relates to the use, of the compoundsaccording to the invention and devices comprising the compounds for thetreatment and prophylaxis of cosmetic conditions.

The present invention furthermore relates to the compounds according tothe invention for the production of devices for the therapy, prophylaxisand/or diagnosis of therapeutic diseases.

Many diseases are associated with cosmetic aspects. Thus, a patient withsevere acne on the face suffers not only from the medical causes andconsequences of the disease, but also from the cosmetic accompanyingcircumstances.

Phototherapy or light therapy is used in many medical and/or cosmeticareas. The compounds according to the invention and the devicescomprising these compounds can therefore be employed for the therapyand/or prophylaxis and/or diagnosis of all diseases and/or in cosmeticapplications for which the person skilled in the art considers the useof phototherapy. Besides irradiation, the term phototherapy alsoincludes photodynamic therapy (PDT) as well as disinfection andsterilisation in general. It is not only humans or animals that can betreated by means of phototherapy or light therapy, but also any othertype of living or non-living materials. These include, for example,fungi, bacteria, microbes, viruses, eukaryotes, pro-karyonts, foods,drinks, water and drinking water.

The term phototherapy also includes any type of combination of lighttherapy and other types of therapy, such as, for example, treatment withactive compounds. Many light therapies have the aim of irradiating ortreating exterior parts of an object, such as the skin of humans andanimals, wounds, mucous membranes, the eye, hair, nails, the nail bed,gums and the tongue. In addition, the treatment or irradiation accordingto the invention can also be carried out inside an object in order, forexample, to treat internal organs (heart, lung, etc.) or blood vesselsor the breast.

The therapeutic and/or cosmetic areas of application according to theinvention are preferably selected from the group of skin diseases andskin-associated diseases or changes or conditions, such as, for example,psoriasis, skin ageing, skin wrinkling, skin rejuvenation, enlarged skinpores, cellulite, oily/greasy skin, folliculitis, actinic keratosis,precancerous actinic keratosis, skin lesions, sun-damaged andsun-stressed skin, crows' feet, skin ulcers, acne, acne rosacea, scarscaused by acne, acne bacteria, photomodulation of greasy/oily sebaceousglands and their surrounding tissue, jaundice, jaundice of the newborn,vitiligo, skin cancer, skin tumours, Crigler-Najjar, dermatitis, atopicdermatitis, diabetic skin ulcers, and desensitisation of the skin.

Particular preference is given for the purposes of the invention to thetreatment and/or prophylaxis of psoriasis, acne, cellulite, skinwrinkling, skin ageing, icterus and vitiligo.

Further areas of application according to the invention for thecompositions and/or devices comprising the compositions according to theinvention are selected from the group of inflammatory diseases,rheumatoid arthritis, pain therapy, treatment of wounds, neurologicaldiseases and conditions, oedema, Paget's disease, primary andmetastasising tumours, connective-tissue diseases or changes, changes inthe collagen, fibroblasts and cell level originating from fibroblasts intissues of mammals, irradiation of the retina, neovascular andhypertrophic diseases, allergic reactions, irradiation of therespiratory tract, sweating, ocular neovascular diseases, viralinfections, particularly infections caused by herpes simplex or HPV(human papillomaviruses) for the treatment of warts and genital warts.

Particular preference is given for the purposes of the invention to thetreatment and/or prophylaxis of rheumatoid arthritis, viral infectionsand pain.

Further areas of application according to the invention for thecompounds and/or devices comprising the compounds according to theinvention are selected from winter depression, sleeping sickness,irradiation for improving the mood, the reduction in pain particularlymuscular pain caused by, for example, tension or joint pain, eliminationof the stiffness of joints and the whitening of the teeth (bleaching).

Further areas of application according to the invention for thecompounds and/or devices comprising the compounds according to theinvention are selected from the group of disinfections. The compoundsaccording to the invention and/or the devices according to the inventioncan be used for the treatment of any type of objects (non-livingmaterials) or subjects (living materials such as, for example, humansand animals) for the purposes of disinfection, sterilisation orpreservation. This includes, for example, the disinfection of wounds,the reduction in bacteria, the disinfection of surgical instruments orother articles, the disinfection or preservation of foods, of liquids,in particular water, drinking water and other drinks, the disinfectionof mucous membranes and gums and teeth. Disinfection here is taken tomean the reduction in the living microbiological causative agents ofundesired effects, such as bacteria and germs.

For the purposes of the phototherapy mentioned above, devices comprisingthe compounds according to the invention preferably emit light having awavelength between 250 and 1250 nm, particularly preferably between 300and 1000 nm and especially preferably between 400 and 850 nm.

In a particularly preferred embodiment of the present invention, thecompounds according to the invention are employed in an organiclight-emitting diode (OLED) or an organic light-emitting electrochemicalcell (OLEC) for the purposes of phototherapy. Both the OLED and the OLECcan have a planar or fibre-like structure having any desired crosssection (for example round, oval, polygonal, square) with a single- ormultilayered structure. These OLECs and/or OLEDs can be installed inother devices which comprise further mechanical, adhesive and/orelectronic elements (for example battery and/or control unit foradjustment of the irradiation times, intensities and wavelengths). Thesedevices comprising the OLECs and/or OLEDs according to the invention arepreferably selected from the group comprising plasters, pads, tapes,bandages, cuffs, blankets, caps, sleeping bags, textiles and stents.

The use of the said devices for the said therapeutic and/or cosmeticpurpose is particularly advantageous compared with the prior art, sincehomogeneous irradiation of lower irradiation intensity is possible atvirtually any site and at any time of day with the aid of the devicesaccording to the invention using the OLEDs and/or OLECs. The irradiationcan be carried out as an inpatient, as an outpatient and/or by thepatient themselves, i.e. without initiation by medical or cosmeticspecialists. Thus, for example, plasters can be worn under clothing, sothat irradiation is also possible during working hours, in leisure timeor during sleep. Complex inpatient/outpatient treatments can in manycases be avoided or their frequency reduced. The devices according tothe invention may be intended for reuse or be disposable articles, whichcan be disposed of after use once, twice or three times.

Further advantages over the prior art are, for example, lower evolutionof heat and emotional aspects. Thus, newborn being treated owing tojaundice typically have to be irradiated blindfolded in an incubatorwithout physical contact with the parents, which represents an emotionalstress situation for parents and newborn. With the aid of a blanketaccording to the invention comprising the OLEDs and/or OLECs accordingto the invention, the emotional stress can be reduced significantly. Inaddition, better temperature control of the child is possible due toreduced heat production of the devices according to the inventioncompared with conventional irradiation equipment.

The compounds according to the invention and the electronic devicesaccording to the invention, in particular organic electroluminescentdevices, are distinguished by the following surprising advantages overthe prior art:

-   1. The compounds according to the invention or compounds of the    formula (1) employed as host or matrix material for fluorescent or    phosphorescent emitters result in very high efficiencies and long    lifetimes. This applies, in particular, if the compounds are    employed as matrix material for a phosphorescent emitter.-   2. The compounds according to the invention or compounds of the    formula (1) are not only suitable as matrix for green- and    red-phosphorescent compounds, but instead also for    blue-phosphorescent compounds.-   3. The compounds according to the invention or compounds of the    formula (1) also exhibit good properties on use as    electron-transport material.-   4. In contrast to many compounds in accordance with the prior art    which exhibit partial or complete pyrolytic decomposition on    sublimation, the compounds according to the invention have high    thermal stability.-   5. The compounds according to the invention, employed in organic    electroluminescent devices, result in high efficiencies and in steep    current/voltage curves with low use voltages.

These above-mentioned advantages are not accompanied by an impairment ofthe other electronic properties.

It should be pointed out that variations of the embodiments described inthe present invention fall within the scope of this invention. Eachfeature disclosed in the present invention can, unless explicitlyexcluded, be replaced by alternative features which serve the same, anequivalent or a similar purpose. Thus, each feature disclosed in thepresent invention should, unless stated otherwise, be regarded as anexample of a generic series or as an equivalent or similar feature.

All features of the present invention can be combined with one anotherin any way, unless certain features and/or steps are mutually exclusive.This applies, in particular, to preferred features of the presentinvention. Equally, features of non-essential combinations can be usedseparately (and not in combination).

It should furthermore be pointed out that many of the features, and inparticular those of the preferred embodiments of the present invention,should be regarded as inventive themselves and not merely as part of theembodiments of the present invention. Independent protection may begranted for these features in addition or as an alternative to eachinvention claimed at present.

The teaching regarding technical action disclosed with the presentinvention can be abstracted and combined with other examples.

The invention is explained in greater detail by the following exampleswithout wishing it to be restricted thereby.

EXAMPLES

The following syntheses are carried out, unless indicated otherwise,under a protective-gas atmosphere in dried solvents. Starting materials(I), (III), (VI), (VII) and (XIII) are commercially available(Sigma-Aldrich, Alessa Syntec, VWR, Carbone Scientific Co., Ltd).

Example 1 Preparation of Compounds (II), (IV), (V), (VIII), (IX) and (X)

Synthetic Procedure for the Preparation of Compound (X):

a) Synthesis of Compound (II)

52 ml (130 mmol) of n-butyllithium (2.5 M in n-hexane) are addeddropwise with vigorous stirring to a suspension of 30.7 g (100 mmol) of4-bromo-benz[a]anthracene (I) in 1000 ml of THF at −78° C., and themixture is stirred for a further 2 h. 16.7 ml (150 mmol) of trimethylborate are added in one portion to the red solution with vigorousstirring, the mixture is stirred at −78° C. for a further 30 min., thenwarmed to room temperature over the course of 3 h, 300 ml of water areadded, and the mixture is stirred for 30 min. The organic phase isseparated off and evaporated to dryness in vacuo. The solid is taken upin 100 ml of n-hexane, filtered off with suction, washed once with 100ml of n-hexane and dried in vacuo. Yield: 23.7 g (87.0 mmol), 87.0%,purity about 90.0% (NMR) of boronic acid, with varying amounts ofboronic anhydride and borinic acid. The boronic acid can be used in thisform without further purification.

b) Synthesis of Compound (IV)

25.0 g (97.2 mmol) of 9-bromoanthracene (III), 27.0 g (99.2 mmol) ofbenz[a]anthracene-4-boronic acid (II) and 44.5 g (210 mmol) oftripotassium phosphate are suspended in 500 ml of toluene, 600 ml ofwater and 100 ml of dioxane. 1.83 g (6.01 mmol) of tri-o-tolylphosphineand then 225 mg (1.00 mmol) of palladium(II) acetate are added to thissuspension, and the mixture is subsequently heated under reflux for 16h. After cooling, the organic phase is separated off, washed three timeswith 500 ml of water, dried using sodium sulfate and subsequentlyevaporated to dryness. The solid is recrystallised from 300 ml oftoluene and finally dried under reduced pressure. The yield is 26.2 g(64.8 mmol), corresponding to 64.8% of theory.

c) Synthesis of Compound (V)

1.30 g (8.02 mmol) of iron(III) chloride and then 13.3 g (74.7 mmol) ofN-bromosuccinimide are added to a suspension, cooled to 0° C., of 26.0 g(64.3 mmol) of compound (IV) in 600 ml of chloroform, and the mixture isstirred at 0° C. for 4 h. After warming to room temperature, 400 ml ofwater are added, the organic phase is separated off, washed three timeswith 300 ml of water, dried using sodium sulfate and subsequentlyevaporated to dryness. The orange solid obtained is recrystallised fromtoluene and finally dried under reduced pressure. The yield is 23.7 g(49.0 mmol), corresponding to 76.6% of theory.

d) Synthesis of Compound (VIII)

8.60 g (159 mmol) of sodium methoxide are stirred for 30 min in 86 ml ofmethanol with 33.0 g (153 mmol) of 3-bromophenylacetic acid (VII) andsubsequently evaporated to dryness. The 3-bromobenzoate formed isrefluxed for 4 h with 30.4 g (76.7 mmol) of 2,4,6-triphenylpyryliumtetrafluoroborate (VI) in 165 ml of acetic anhydride. After cooling, theacetic anhydride is removed by distillation, the residue is taken up in400 ml of dichloromethane and washed twice with 200 ml of water eachtime, dried using sodium sulfate and subsequently evaporated to dryness.The dark-green liquid is filtered through silica gel with aheptane/ethyl acetate mixture (9:1), corresponding fractions areevaporated to dryness. The orange solid obtained is recrystallised fromethanol and finally dried under reduced pressure. The yield is 18.1 g(39.2 mmol), corresponding to 51.1% of theory.

e) Synthesis of Compound (IX)

8.80 ml (22.0 mmol) of n-butyllithium (2.5 M in n-hexane) are addeddropwise with vigorous stirring to a suspension of 10.0 g (21.7 mmol) ofcompound (VIII) in 500 ml of THF at −78° C., and the mixture is stirredfor a further 1 h. 5.10 ml (22.2 mmol) of triisopropyl borate are addedin one portion to the solution with vigorous stirring, the mixture isstirred at −78° C. for a further 2 h, then warmed to room temperatureover the course of 1 h. After cooling to 0° C., 200 ml of 0.2 Nhydrochloric acid are added dropwise, and 300 ml of ethyl acetate areadded. The aqueous phase is separated off, extracted twice with 200 mlof ethyl acetate, the combined organic phases are washed once with 200ml of water, once with 200 ml of saturated sodium hydrogencarbonatesolution and once with 200 ml of saturated sodium chloride solution,dried using sodium sulfate and subsequently evaporated to dryness. Thecolourless solid obtained is stirred in a hot heptane/toluene mixture,filtered off with suction and finally dried under reduced pressure. Theyield is 7.08 g (16.6 mmol), corresponding to 76.2% of theory.

f) Synthesis of Compound (X)

900 mg (1.86 mmol) of compound (V), 880 mg (2.06 mmol) of compound (IX)and 3.50 ml of a 2.0 M sodium carbonate solution (7.00 mmol) aresuspended in 15 ml of toluene and 15 ml of ethanol. 30.0 mg (26.0 μmol)of tetrakis(triphenylphosphine)palladium(0) are added to thissuspension, and the mixture is subsequently heated under reflux for 16h. After cooling, the organic phase is separated off, washed three timeswith 20 ml of water and once with 20 ml of saturated sodium chloridesolution, dried using sodium sulfate and subsequently evaporated todryness. The residue is filtered through silica gel with a heptane/ethylacetate mixture (9:1), corresponding fractions are evaporated todryness. The solid obtained is recrystallised twice from atoluene/ethanol mixture and finally dried under reduced pressure. Theyield is 1.18 g (1.50 mmol), corresponding to 78.7% of theory.

Example 2 Preparation of Compounds (XI), (XII) and (XIV) to (XVIII)

Synthetic Procedure for the Preparation of Compound (XVIII):

a) Synthesis of Compound (XI)

2.70 g (10.5 mmol) of 9-bromoanthracene (III), 5.00 g (11.7 mmol) ofcompound (IX) and 3.90 g (36.8 mmol) of sodium carbonate are suspendedin 60 ml of toluene, 60 ml of ethanol and 14 ml of water. 130 mg (0.112mmol) of tetrakis(triphenylphosphine)palladium(0) are added to thissuspension, and the mixture is subsequently heated under reflux for 16h. After cooling, the organic phase is separated off, washed three timeswith 50 ml of water, dried using sodium sulfate and subsequentlyevaporated to dryness. The solid is recrystallised from toluene andfinally dried under reduced pressure. The yield is 5.19 g (9.29 mmol),corresponding to 88.5% of theory.

b) Synthesis of Compound (XII)

150 mg (0.925 mmol) of iron(III) chloride and then 1.90 g (10.7 mmol) ofN-bromosuccinimide are added to a suspension, cooled to 0° C., of 5.00 g(8.95 mmol) of compound (XI) in 90 ml of chloroform, and the mixture isstirred at 0° C. for 2 h. After warming to room temperature, 100 ml ofwater are added, the organic phase is separated off, washed three timeswith 50 ml of water, dried using sodium sulfate and subsequentlyevaporated to dryness. The solid obtained is recrystallised from aheptane/ethyl acetate mixture and finally dried under reduced pressure.The yield is 4.30 g (6.74 mmol), corresponding to 75.4% of theory.

c) Synthesis of Compound (XIV)

200 g (908 mmol) of 3-acetylphenanthrene (XIII), 167 g (2.36 mol) ofhydroxylammonium chloride and 257 ml (3.18 mmol) of pyridine aresuspended in 800 ml of ethanol and refluxed at a bath temperature of100° C. for 2 h. After cooling, 700 ml of ethyl acetate and 700 ml ofwater are added, the organic phase is separated off, washed three timeswith 500 ml of water, dried using sodium sulfate and subsequentlyevaporated to dryness. The residue is washed by stirring in 500 ml ofethanol and finally dried under reduced pressure. The yield is 160 g(682 mmol), corresponding to 75.1% of theory.

d) Synthesis of Compound (XV)

1.50 kg (15.3 mol) of polyphosphoric acid are heated to 100° C., 160 g(680 mmol) of compound (XIV) are added in portions over the course ofone hour, and the mixture is stirred at 100° C. for a further 20 min.After cooling, 1000 ml of ice-water are carefully added, and the mixtureis stirred at room temperature for 30 min. The solid formed is filteredoff with suction, rinsed with water and dried under reduced pressure.200 ml of 37% hydrochloric acid and 2.50 l of methanol are added to thesolid, and the mixture is refluxed for 16 h. The majority of themethanol is removed under reduced pressure, the pale-green solid isfiltered off with suction. This is suspended in 500 ml of water,neutralised using 300 ml of 30% NaOH solution and extracted three timeswith 300 ml of ethyl acetate each time. The combined organic phases arewashed twice with 300 ml of water, dried using sodium sulfate andsubsequently evaporated to dryness. The residue is filtered throughsilica gel with a heptane/ethyl acetate mixture (3:1), correspondingfractions are evaporated and finally dried under reduced pressure. Theyield is 82.0 g (423 mmol), corresponding to 62.3% of theory.

e) Synthesis of Compound (XVI)

82.0 g (423 mmol) of phenanthren-3-ylamine (XV) and 95.0 g (425 mmol) ofcopper(II) bromide are suspended in 1.70 l of acetonitrile and cooled to0° C. 100 ml (1.33 mol) of tert-butyl nitrite are added dropwise overthe course of 45 min at such a rate that an internal temperature of 5°C. was not exceeded, and the mixture is stirred at 0° C. for a further 1h. The batch is added to 1.50 kg of ice, stirred for a further 30 min,the dark-brown solid is filtered off with suction and discarded. 1000 mlof ethyl acetate are added to the mother liquor, the organic phase isseparated off, washed twice with 500 ml of 2 N HCl each time and twicewith 500 ml of water each time, dried using sodium sulfate andsubsequently evaporated to dryness. The residue is filtered throughsilica gel with a heptane/ethyl acetate mixture (10:1), correspondingfractions are evaporated and finally dried under reduced pressure. Theyield is 35.9 g (140 mmol), corresponding to 32.9% of theory.

f) Synthesis of Compound (XVII)

35.6 g (138 mmol) of 3-bromophenanthrene (XVI), 42.0 g (165 mmol) ofbispinacolatodiboron and 46.0 g (469 mmol) of potassium acetate aresuspended in 500 ml of dimethyl sulfoxide. 3.50 g (4.29 mmol) of1,1-bis-(diphenylphosphino)ferrocenepalladium(II) dichloride*DCM areadded to this suspension, and the reaction mixture is stirred at 80° C.for 6 h. After cooling, 1000 ml of ethyl acetate and 1000 ml of waterare added, the organic phase is separated off, washed three times with300 ml of water each time, dried using sodium sulfate and subsequentlyevaporated to dryness. The crude product is passed through a silica-gelcolumn with a heptane/ethyl acetate mixture (10:1), correspondingfractions are evaporated and finally dried under reduced pressure. Theyield is 38.5 g (127 mmol), corresponding to 92.0% of theory.

g) Synthesis of Compound (XVIII)

4.20 g (6.59 mmol) of compound (XII), 2.20 g (7.23 mmol) of compound(XVII) and 2.50 g (23.6 mmol) of sodium carbonate are suspended in 40 mlof toluene, 40 ml of ethanol and 10 ml of water. 100 mg (87.0 μmol) oftetrakis(triphenylphosphine)palladium(0) are added to this suspension,and the mixture is subsequently heated under reflux for 16 h. Aftercooling, the organic phase is separated off, washed three times with 50ml of water and once with 50 ml of saturated sodium chloride solution,dried using sodium sulfate and subsequently evaporated to dryness. Theresidue is recrystallised from a heptane/toluene mixture and extractedwith hot toluene. The yield is 4.08 g (5.55 mmol), corresponding to84.3% of theory.

Example 3 Comparative Example Preparation of Compound (XX)

Synthetic Procedure for the Preparation of Compound (XX)

The synthesis of compound (XX) is carried out analogously to that ofcompound (X), with compound (IX) being replaced by 880 mg (2.06 mmol) ofcompound (XIX). The yield is 1.10 g (1.40 mmol), corresponding to 75.3%of theory.

Example 4 Comparative Example Preparation of Compound (XXIV)

Synthetic Procedure for the Preparation of Compound (XXIV)

a) Synthesis of Compound (XXII)

The synthesis of compound (XXII) is carried out analogously to that ofcompound (XI), with compound (IX) being replaced by 5.00 g (11.7 mmol)of compound (XXI). The yield is 5.01 g (8.96 mmol), corresponding to85.4% of theory.

b) Synthesis of Compound (XXIII)

The synthesis of compound (XXIII) is carried out analogously to that ofcompound (XII), with compound (XI) being replaced by 5.00 g (8.95 mmol)of compound (XXII). The yield is 4.46 g (6.99 mmol), corresponding to78.1% of theory.

c) Synthesis of Compound (XXIV)

The synthesis of compound (XXIV) is carried out analogously to that ofcompound (XVIII), with compound (XII) being replaced by 4.20 g (6.59mmol) of compound (XXII). The yield is 4.03 g (5.48 mmol), correspondingto 83.2% of theory.

Example 5 Production and Characterisation of Fluorescent OrganicElectroluminescent Devices Comprising the Compounds According to theInvention

The structures of SEB-1 (synthesised in accordance with WO 08/006,449)and ETM-1 (WO 2005/053055) are depicted below for the sake of clarity.

The materials according to the invention can be used from solution,where they result in simple devices having nevertheless very goodproperties. The devices described are produced using techniques whichare very well known to the person skilled in the art in the area. Theproduction of such components is based on the production of polymericlight-emitting diodes (PLEDs), which has already been described manytimes in the literature (for example in WO 2004/037887). In the presentcase, compounds (X) and (XVIII) according to the invention or thelikewise soluble comparative compounds (XX) and (XXIV) are dissolved intoluene. The emitter proportion is 5% by weight. The typical solidscontent of such solutions is 15 g/l.

The structure of the device is as follows: cathode (Al 100 nm)/ETL (20nm)/EML (50 nm)/interlayer (20 nm)/buffer layer (PEDOT:PSS, 20nm)/anode, where ETL is the electron-transport layer, which comprises20% by weight of compound ETM-1 and 80% by weight of Liq, and EMLrepresents the emitting layer. The emitting layer comprises 95% byweight of the host material according to the invention and 5% by weightof emitter SEB-1. Structured ITO substrates (Technoprint) and thematerial for the so-called buffer layer (PEDOT:PSS) (as Clevios BaytronP aqueous dispersion from H.C. Starck) are commercially available. Theinterlayer used serves for hole injection; in this case, HIL-012 fromMerck KGaA is used. The emission layer is applied by spin coating in aninert-gas atmosphere, in the present case argon, and dried by heating at120° C. for 10 min. Finally, an aluminium cathode is applied by vacuumvapour deposition. A hole-blocking layer and/or an electron-transportlayer can also be applied between the emitting layer and the cathode byvapour deposition, and the interlayer can also be replaced by one ormore layers, which merely have to satisfy the condition of not beingdetached again by the subsequent processing step of deposition of theemitting layer from solution.

The devices are characterised as standard by means of methods which arewell known to the person skilled in the art. The OLED examples givenhave not yet been optimised. Table 1 summarises the data obtained. Inthe case of the processed devices, it is apparent that the materialsaccording to the invention are superior to those previously available interms of efficiency and/or lifetime.

TABLE 1 Results with solution-processed materials according to theinvention in the device configuration described(Ba/Al)/EML/interlayer/buffer layer/ITO. Lifetime [h], Max. Voltageinitial EML eff. [V] at CIE luminance Ex. 50 nm [cd/A] 1000 cd/m² (x, y)1000 cd/m² 3 comp. (XX): 4.5 4.9 0.14, 0.18 300 SEB-1 1 (X): 5.9 4.80.14, 0.18 500 SEB-1 4 comp. (XXIV): 4.4 4.8 0.14, 0.18 350 SEB-1 2(XVIII): 6.1 4.8 0.14, 0.18 600 SEB-1

Example 6 Preparation of Compound (XXVI)

Synthetic Procedure for the Preparation of Compound (XXVI)

10.0 g (20 mmol) of4,4,5,5-tetramethyl-2-(3-(2,4,6-triphenyl)phenyl)phenyl-1,3,2-dioxaborolaneand 500 ml of toluene are added to a solution of 33.0 g (310 mol) ofsodium carbonate in dist. water (3 ml). One drop of Aliquat, 5.0 g ofcompound (XXV) (19 mmol) and subsequently 0.2 g oftetrakis(triphenylphosphine)palladium (0.2 mmol) is to the reactionmixture. The reaction mixture is stirred at 90° C. for two days. Afteraddition of 150 ml of dichloromethane, the organic phase is washed witha sodium chloride solution (sat.), dried over magnesium sulfate andsubsequently evaporated to dryness. The residue is purified by columnchromatography over silica gel (CH:DCM=4:1). The product is subsequentlydissolved in dichloromethane and precipitated from methanol. Thecolourless solid is dissolved in boiling toluene and re-precipitated byaddition of n-pentane. The yield is 5.0 g (8 mmol), corresponding to41.0% of theory.

Example 7 Comparative Example Preparation of Compounds (XXVII) to (XXIX)

Synthetic Procedure for the Preparation of Compound (XXIX)

a) Synthesis of Compound (XXVII)

The synthesis of compound (XXVII) is carried out analogously to that ofcompound (VIII), with the 3-bromophenylacetic acid being replaced by42.2 g (195 mmol) of 4-bromophenylacetic acid. The yield is 23.2 g (50.2mmol), corresponding to 50.9% of theory.

b) Synthesis of Compound (XXVIII)

The synthesis of compound (XXVIII) is carried out analogously to that ofcompound (IX), with compound (VIII) being replaced by 20.0 g (43.4 mmol)by compound (XXVII). The yield is 14.20 g (33.2 mmol), corresponding to76.2% of theory.

c) Synthesis of Compound (XXIX)

The synthesis of compound (XXIX) is carried out analogously to that ofcompound (XXVI), with compound (IX) being replaced by 12.0 g (45.5 mmol)of compound (XXVIII). The yield is 12.1 g (19.1 mmol), corresponding to42.0% of theory.

Example 8 Production and Characterisation of Phosphorescent OrganicElectroluminescent Devices Comprising the Compounds According to theInvention

The structures of emitter TEG-1 (synthesised in accordance with WO2004/085449) and co-host C1 (in accordance with WO 2009/124627) aredepicted below for the sake of clarity.

The materials according to the invention can be used from solution,where they result in simple devices having nevertheless very goodproperties. The devices described are produced using techniques whichare very well known to the person skilled in the art in the area. Theproduction of such components is based on the production of polymericlight-emitting diodes (PLEDs), which has already been described manytimes in the literature (for example in WO 2004/037887). In the presentcase, the compounds according to the invention (for example the compoundof the formula (XXVI)) or the likewise soluble comparative compounds(XXIX) are dissolved in toluene. The typical solids content of suchsolutions is between 16 and 25 g/l, if, as here, the typical layerthickness of 80 nm for a device is to be achieved by means of spincoating. The structure of the device is as follows: cathode (Ba/Al:3nm/150 nm)/EML (80 nm)/interlayer (20 nm)/buffer layer (PEDOT:PSS, 80nm)/anode, where EML represents the emitting layer, which, in thepresent case, comprises either 83% by weight of the matrix material(XXVI or XXIX) or 41.5% by weight of the matrix material (XXVI or XXIX)and 41.5% by weight of co-host C1, and 17% by weight of the emitter.Structured ITO substrates (Technoprint) and the material for theso-called buffer layer (PEDOT:PSS) (as Clevios Baytron P aqueousdispersion from H.C. Starck) are commercially available. The interlayerused serves for hole injection; in this case, HIL-012 from Merck KGaA isused. The emission layer is applied by spin coating in an inert-gasatmosphere, in the present case argon, and dried by heating at 120° C.for 10 min. Finally, a barium and aluminium cathode is applied by vacuumvapour deposition. A hole-blocking layer and/or an electron-transportlayer can also be applied between the emitting layer and the cathode byvapour deposition, and the interlayer can also be replaced by one ormore layers, which merely have to satisfy the condition of not beingdetached again by the subsequent processing step of deposition of theemitting layer from solution.

The devices are characterised as standard by means of methods which arewell known to the person skilled in the art. The OLED examples givenhave not yet been optimised. Table 2 summarises the data obtained. Inthe case of the processed devices, it is apparent that the materialsaccording to the invention are superior to those previously available interms of efficiency and/or lifetime.

TABLE 2 Results with solution-processed materials according to theinvention in the phosphorescent device configuration described(Ba/Al)/EML/interlayer/buffer layer/ITO. Lifetime [h], Max. Voltageinitial EML eff. [V] at CIE luminance Ex. 80 nm [cd/A] 1000 cd/m² (x, y)1000 cd/m² 7 comp. (XXIX): 12 4.7 0.33/0.63 8000 TEG-1 6 (XXVI): 20 4.60.33/0.63 18000 TEG-1 7 comp. (XXIX): 15 4.6 0.33/0.63 12000 C1: TEG-1 6(XXVI): 34 4.6 0.33/0.63 37000 C1: TEG-1

The invention claimed is:
 1. A compound of the formula (2)

where the following applies to the symbols and indices used: X is oneach occurrence; Y is CR¹; R¹ is, identically or differently on eachoccurrence, H, D, F, Cl, Br, I, N(R²)₂, CN, NO₂, Si(R²)₃, B(OR²)₂,C(═O)R², P(═O)(R²)₂, S(═O)R², S(═O)₂R², OSO₂R², a straight-chain alkyl,alkoxy or thioalkoxy group having 1 to 40 C atoms or a straight-chainalkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclicalkyl, alkenyl, alkynyl, alkoxy, alkylalkoxy or thioalkoxy group having3 to 40 C atoms, each of which is optionally substituted by one or moreradicals R², where one or more non-adjacent CH₂ groups is optionallyreplaced by R²C═CR², C≡C, Si(R²)₂, Ge(R²)₂, Sn(R²)₂, C═O, C═S, C═Se,C═NR², P(═O)(R²), SO, SO₂, NR², O, S or CONR² and where one or more Hatoms is optionally replaced by D, F, Cl, Br, I, CN or NO₂, or anaromatic or heteroaromatic ring system having 5 to 60 aromatic ringatoms, which may in each case be substituted by one or more radicals R²,or an aryloxy, arylalkoxy or heteroaryloxy group having 5 to 60 aromaticring atoms, which is optionally substituted by one or more radicals R²,or a diarylamino group, diheteroarylamino group or arylheteroarylaminogroup having 10 to 40 aromatic ring atoms, which is optionallysubstituted by one or more radicals R², or a combination of two or moreof these groups or a crosslinkable group Q; R² is, identically ordifferently on each occurrence, H, D, F, Cl, Br, I, N(R³)₂, CN, NO₂,Si(R³)₃, B(OR³)₂, C(═O)R³, P(═O)(R³)₂, S(═O)R³, S(═O)₂R³, OSO₂R³, astraight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atomsor a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms or abranched or cyclic alkyl, alkenyl, alkynyl, alkoxy, alkylalkoxy orthioalkoxy group having 3 to 40 C atoms, each of which is optionallysubstituted by one or more radicals R³, where one or more non-adjacentCH₂ groups is optionally replaced by R³C═CR³, C≡C, Si(R³)₂, Ge(R³)₂,Sn(R³)₂, C═O, C═S, C═Se, C═NR³, P(═O)(R³), SO, SO₂, NR³, O, S or CONR³and where one or more H atoms is optionally replaced by D, F, Cl, Br, I,CN or NO₂, or an aromatic or heteroaromatic ring system having 5 to 60aromatic ring atoms, which may in each case be substituted by one ormore radicals R³, or an aryloxy, arylalkoxy or heteroaryloxy grouphaving 5 to 60 aromatic ring atoms, which is optionally substituted byone or more radicals R³, or a diarylamino group, diheteroarylamino groupor arylheteroarylamino group having 10 to 40 aromatic ring atoms, whichis optionally substituted by one or more radicals R³, or a combinationof two or more of these groups; two or more adjacent radicals R² heremay form a mono- or polycyclic, aliphatic or aromatic ring system withone another; R³ is, identically or differently on each occurrence, H, D,F or an aliphatic, aromatic and/or heteroaromatic hydrocarbon radicalhaving 1 to 20 C atoms, in which, in addition, one or more H atoms isoptionally replaced by F; two or more substituents R³ here may also forma mono- or polycyclic, aliphatic or aromatic ring system with oneanother; and Z is on each occurrence, identically or differently, R¹,with the proviso that at least one of the radicals Z must be an aromaticor heteroaromatic group having 5 to 60 aromatic ring atoms; and q, r, sand t is, independently of one another, either 0 or 1 and u=q+r+s+t=1,2, 3 or
 4. 2. The compound according to claim 1, wherein the compoundhas the formula (18)


3. The compound according to claim 1, wherein the compound has theformula (20)


4. The compound according to claim 1, wherein Z, identically ordifferently on each occurrence, H, D, F, Cl, Br, I, N(R²)₂, CN, NO₂,Si(R²)₃, B(OR²)₂, C(═O)R², P(═O)(R²)₂, S(═O)R², S(═O)₂R², OSO₂R², astraight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atomsor a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms or abranched or cyclic alkyl, alkenyl, alkynyl, alkoxy, alkylalkoxy orthioalkoxy group having 3 to 40 C atoms, each of which is optionallysubstituted by one or more radicals R², where one or more non-adjacentCH₂ groups is optionally replaced by R²C═CR², Si(R²)₂, Ge(R²)₂, Sn(R²)₂,C═O, C═S, C═Se, C═NR², P(═O)(R²), SO, SO₂, NR², O, S or CONR² and whereone or more H atoms is optionally replaced by D, F, Cl, Br, I, CN orNO₂, or an aromatic or heteroaromatic ring system having 5 to 60aromatic ring atoms, which may in each case be substituted by one ormore radicals R², or an aryloxy, arylalkoxy or heteroaryloxy grouphaving 5 to 60 aromatic ring atoms, which is optionally substituted byone or more radicals R², or a diarylamino group, diheteroarylamino groupor arylheteroarylamino group having 10 to 40 aromatic ring atoms, whichis optionally substituted by one or more radicals R², or a combinationof two or more of these groups, with the proviso that at least one ofthe radicals Z occurring must be an aromatic or heteroaromatic grouphaving 5 to 60 aromatic ring atoms.
 5. The compound according to claim1, wherein Z is, identically or independently of one another on eachoccurrence, an aromatic or heteroaromatic group having 5 to 60 aromaticring atoms, where the group of the aromatic and heteroaromatic groupshaving 5 to 60 ring atoms also include condensed aromatic andheteroaromatic ring systems.
 6. The compound according to claim 1,wherein Z is selected from the group of the radicals having thefollowing formulae (66) to (80)

where Y is on each occurrence, identically or differently, CR¹, N, P orPR¹ ₂.
 7. The compound according to claim 6, wherein Y is on eachoccurrence, identically or differently, CR¹ or N.
 8. A formulationcomprising at least one compound according to claim 1 and at least onesolvent.
 9. A composition comprising at least one of the compoundsaccording to claim 1 and at least one further organically functionalmaterial selected from the group consisting of the emitters, hostmaterials, matrix materials, electron-transport materials (ETM),electron-injection materials (EIM), hole-transport materials (HTM),hole-injection materials (HIM), electron-blocking materials (EBM),hole-blocking materials (HBM) and exciton-blocking materials (ExBM). 10.A composition comprising at least one of the compounds according toclaim 1 and at least one further organically functional materialselected from the group consisting of fluorescent and phosphorescentemitters.
 11. A process for the therapy and/or diagnosis of diseasesand/or cosmetic conditions which comprises utilizing the compoundaccording to claim 1.